Plasma enhanced atomic layer deposition system and method

ABSTRACT

A method for depositing a film on a substrate using a plasma enhanced atomic layer deposition (PEALD) process includes disposing the substrate in a process chamber configured to facilitate the PEALD process, introducing a first process material within the process chamber and introducing a second process material within the process chamber. Also included is coupling electromagnetic power to the process chamber during introduction of the second process material in order to generate a plasma that facilitates a reduction reaction between the first and second process materials at a surface of the substrate. A reactive gas is introduced within the process chamber, the reactive gas chemically reacting with contaminants in the process chamber to release the contaminants from at least one of a process chamber component or the substrate.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a plasma enhanced atomic layerdeposition system and a method of operating thereof, and moreparticularly to a plasma enhanced atomic layer deposition system havingreduced contamination.

2. Description of Related Art

Typically, during materials processing, plasma is employed to facilitatethe addition and removal of material films when fabricating compositematerial structures. For example, in semiconductor processing, a (dry)plasma etch process is utilized to remove or etch material along finetrenches or within vias or contacts patterned on a silicon substrate.Alternatively, for example, a vapor deposition process is utilized todeposit material along fine lines or within vias or contacts on asilicon substrate. In the latter, vapor deposition processes includechemical vapor deposition (CVD), and plasma enhanced chemical vapordeposition (PECVD).

In PECVD, plasma is utilized to alter or enhance the film depositionmechanism. For instance, plasma excitation generally allows film-formingreactions to proceed at temperatures that are significantly lower thanthose typically required to produce a similar film by thermally excitedCVD. In addition, plasma excitation may activate film-forming chemicalreactions that are not energetically or kinetically favored in thermalCVD. The chemical and physical properties of PECVD films may thus bevaried over a relatively wide range by adjusting process parameters.

More recently, atomic layer deposition (ALD), a form of CVD or moregenerally film deposition, has emerged as a candidate for ultra-thingate film formation in front end-of-line (FEOL) operations, as well asultra-thin barrier layer and seed layer formation for metallization inback end-of-line (BEOL) operations. In ALD, two or more process gassesare introduced alternatingly and sequentially in order to form amaterial film one monolayer at a time. Such an ALD process has proven toprovide improved uniformity and control in layer thickness, as well asconformality to features on which the layer is deposited. However,current ALD processes generally have a slow deposition rate that is notfeasible for production requirements. Moreover, current ALD processesoften suffer from contamination problems that affect the quality of thedeposited films, and thus the manufactured device. Factors such as thesehave been an impediment to wide acceptance of ALD films despite theirsuperior characteristics.

SUMMARY OF THE INVENTION

Accordingly, one object of the present invention is directed toaddressing any of the above-described and/or other problems with ALDsystems and processes.

Another object of the present invention is to reduce contaminationproblems relating to deposition of ALD films.

These and/or other objects of the present invention may be provided by amethod for depositing a film on a substrate using a plasma enhancedatomic layer deposition (PEALD) process. In one aspect of the invention,the method includes disposing the substrate in a process chamberconfigured to facilitate the PEALD process, introducing a first processmaterial within the process chamber and introducing a second processingmaterial within the process chamber. Also included is couplingelectromagnetic power to the process chamber during introduction of thesecond process material in order to generate a plasma that facilitates areduction reaction between the first and second process materials at asurface of the substrate, and introducing within the process chamber areactive gas that chemically reacts with contaminants in the processchamber to release the contaminants from at least one of a processchamber component or the substrate.

Another aspect of the invention includes an atomic layer depositionsystem having a process chamber, a substrate holder provided within theprocess chamber and configured to support a substrate, a first processmaterial supply system configured to supply a first process material tothe process chamber and a second process material supply systemconfigured to supply a second process material to the process chamber.Also included is a power source configured to couple electromagneticpower to the process chamber during introduction of the second processmaterial in order to generate a plasma that facilitates a reductionreaction between the first and second process materials at a surface ofthe substrate. A reactive purge gas supply system is configured tointroduce within the process chamber a reactive gas that chemicallyreacts with contaminants in the process chamber to release thecontaminants from at least one of a process chamber component or thesubstrate.

In still another aspect of the invention, an atomic layer depositionsystem includes a process chamber, means provided within the processchamber for supporting a substrate, means for introducing a firstprocess material within the process chamber and means for introducing asecond process material within the process chamber. Also included ismeans for coupling electromagnetic power to the process chamber duringintroduction of the second process material in order to generate aplasma that facilitates a reduction reaction between the first andsecond process materials at a surface of the substrate. Finally,included is means for introducing within the process chamber a reactivegas that chemically reacts with contaminants in the process chamber torelease the contaminants from at least one of a process chambercomponent or the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. 1A depicts a schematic view of a deposition system in accordancewith an embodiment of the invention;

FIG. 1B depicts a schematic view of another deposition system inaccordance with an embodiment of the invention;

FIG. 2A depicts a schematic view of a deposition system in accordancewith an embodiment of the invention;

FIG. 2B depicts a schematic view of another deposition system inaccordance with an embodiment of the invention;

FIG. 3 is a timing diagram for an ALD process according to an embodimentof the invention;

FIGS. 4A-4C present exemplary ALD process data;

FIG. 5 shows a process flow diagram of an ALD process in accordance withan embodiment of the present invention;

FIG. 6 shows a process flow diagram of an ALD process in accordance withanother embodiment of the present invention;

FIGS. 7A and 7B show power graphs depicting the power level variation ofa power coupled to the processing chamber to generate cleaning andreduction reaction plasmas in accordance with embodiments of the presentinvention;

FIG. 8 shows a process flow diagram of an ALD process in accordance withan embodiment of the present invention;

FIGS. 9A-C illustrate a substrate zone and a peripheral zone in a PEALDprocess chamber, and two timing sequences for plasma in the substratezone and plasma in the peripheral zone according to an embodiment of thepresent invention;

FIGS. 10A-10D depict peripheral electrode assemblies according toembodiments of the present invention;

FIGS. 11A-11D depict peripheral inductive electrode assemblies accordingto embodiments of the present invention;

FIG. 12 shows a process flow diagram of an ALD process in accordancewith an embodiment of the present invention;

FIG. 13 shows a process flow diagram of an ALD process in accordancewith an embodiment of the present invention;

FIG. 14 shows a process flow diagram of a substrate process inaccordance with an embodiment of the present invention;

FIG. 15 is a simplified block diagram of a processing tool forprocessing a substrate in accordance with an embodiment of the presentinvention; and

FIG. 16 is a simplified block-diagram of a plasma processing systemcontaining a slot plane antenna (SPA) plasma source for generating asoft plasma for reducing contaminants on an ALD layer.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the following description, in order to facilitate a thoroughunderstanding of the invention and for purposes of explanation and notlimitation, specific details are set forth, such as a particulargeometry of the deposition system and descriptions of variouscomponents. However, it should be understood that the invention may bepracticed in other embodiments that depart from these specific details.

Referring now to the drawings, wherein like reference numerals designateidentical or corresponding parts throughout the several views, FIG. 1Aillustrates a deposition system 1 for depositing a thin film on asubstrate according to one embodiment. For example, during themetallization of inter-connect and intra-connect structures forsemiconductor devices in back-end-of-line (BEOL) operations, a thinconformal barrier layer may be deposited on wiring trenches or vias tominimize the migration of metal into the inter-level or intra-leveldielectric. Further, a thin conformal seed layer may be deposited onwiring trenches or vias to provide a film with acceptable adhesionproperties for bulk metal fill, or a thin conformal adhesion layer maybe deposited on wiring trenches or vias to provide a film withacceptable adhesion properties for metal seed deposition. Infront-end-of line (FEOL) operations, the deposition system 1 may be usedto deposit an ultra thin gate layer, and/or a gate dielectric layer suchas a high dielectric constant (high-K) film.

The deposition system 1 comprises a process chamber 10 having asubstrate holder 20 configured to support a substrate 25, upon which thethin film is formed. The process chamber 10 further comprises an upperassembly 30 coupled to a first process material supply system 40, asecond process material supply system 42, and a purge gas supply system44. Additionally, the deposition system 1 comprises a first power source50 coupled to the process chamber 10 and configured to generate plasmain the process chamber 10, and a substrate temperature control system 60coupled to substrate holder 20 and configured to elevate and control thetemperature of substrate 25. Additionally, deposition system 1 comprisesa controller 70 that can be coupled to process chamber 10, substrateholder 20, upper assembly 30, first process material supply system 40,second process material supply system 42, purge gas supply system 44,first power source 50, and substrate temperature control system 60.

Alternately, or in addition, controller 70 can be coupled to one or moreadditional controllers/computers (not shown), and controller 70 canobtain setup and/or configuration information from an additionalcontroller/computer.

In FIG. 1A, singular processing elements (10, 20, 30, 40, 42, 44, 50,and 60) are shown, but this is not required for the invention. Thedeposition system 1 can comprise any number of processing elementshaving any number of controllers associated with them in addition toindependent processing elements.

The controller 70 can be used to configure any number of processingelements (10, 20, 30, 40, 42, 44, 50, and 60), and the controller 70 cancollect, provide, process, store, and display data from processingelements. The controller 70 can comprise a number of applications forcontrolling one or more of the processing elements. For example,controller 70 can include a graphic user interface (GUI) component (notshown) that can provide easy to use interfaces that enable a user tomonitor and/or control one or more processing elements.

Referring still to FIG. 1A, the deposition system 1 may be configured toprocess 200 mm substrates, 300 mm substrates, or larger-sizedsubstrates. In fact, it is contemplated that the deposition system maybe configured to process substrates, wafers, or LCDs regardless of theirsize, as would be appreciated by those skilled in the art. Therefore,while aspects of the invention will be described in connection with theprocessing of a semiconductor substrate, the invention is not limitedsolely thereto.

The first process material supply system 40 and the second processmaterial supply system 42 are configured to alternatingly introduce afirst process material to process chamber 10 and a second processmaterial to process chamber 10. The alternation of the introduction ofthe first material and the introduction of the second material can becyclical, or it may be acyclical with variable time periods betweenintroduction of the first and second process materials. The firstprocess material can, for example, comprise a film precursor, such as acomposition having the principal atomic or molecular species found inthe film formed on substrate 25. For instance, the film precursor canoriginate as a solid phase, a liquid phase, or a gaseous phase, and itmay be delivered to process chamber 10 in a gaseous phase with orwithout the use of a carrier gas. The second process material can, forexample, comprise a reducing agent, which may also include atomic ormolecular species found in the film formed on substrate 25. Forinstance, the reducing agent can originate as a solid phase, a liquidphase, or a gaseous phase, and it may be delivered to process chamber 10in a gaseous phase with or without the use of a carrier gas.

Additionally, the purge gas supply system 44 can be configured tointroduce a purge gas to process chamber 10. For example, theintroduction of purge gas may occur between introduction of the firstprocess material and the second process material to process chamber 10,or following the introduction of the second process material to processchamber 10, respectively. The purge gas can comprise an inert gas, suchas a Noble gas (i.e., helium, neon, argon, xenon, krypton), or nitrogen,or hydrogen. In one embodiment, the purge gas supply system 44 can alsobe configured to introduce a reactive purge gas as will be describedbelow.

Referring still to FIG. 1A, the deposition system 1 comprises a plasmageneration system configured to generate a plasma during at least aportion of the alternating introduction of the first process materialand the second process material to process chamber 10. The plasmageneration system can include a first power source 50 coupled to theprocess chamber 10, and configured to couple power to the first processmaterial, or the second process material, or both in process chamber 10.The first power source 50 may be a variable power source and may includea radio frequency (RF) generator and an impedance match network, and mayfurther include an electrode through which RF power is coupled to theplasma in process chamber 10. The electrode can be formed in the upperassembly 30, and it can be configured to oppose the substrate holder 20.The impedance match network can be configured to optimize the transferof RF power from the RF generator to the plasma by matching the outputimpedance of the match network with the input impedance of the processchamber, including the electrode, and plasma. For instance, theimpedance match network serves to improve the transfer of RF power toplasma in plasma process chamber 10 by reducing the reflected power.Match network topologies (e.g. L-type, π-type, T-type, etc.) andautomatic control methods are well known to those skilled in the art.

Alternatively, the first power source 50 may include a radio frequency(RF) generator and an impedance match network, and may further includean antenna, such as an inductive coil, through which RF power is coupledto plasma in process chamber 10. The antenna can, for example, include ahelical or solenoidal coil, such as in an inductively coupled plasmasource or helicon source, or it can, for example, include a flat coil asin a transformer coupled plasma source.

Alternatively, the first power source 50 may include a microwavefrequency generator, and may further include a microwave antenna andmicrowave window through which microwave power is coupled to plasma inprocess chamber 10. The coupling of microwave power can be accomplishedusing electron cyclotron resonance (ECR) technology, or it may beemployed using surface wave plasma technology, such as a slotted planeantenna (SPA), as described in U.S. Pat. No. 5,024,716, entitled “Plasmaprocessing apparatus for etching, ashing, and film-formation”; thecontents of which are herein incorporated by reference in its entirety.

Optionally, the plasma generation system includes a first electrode inthe upper assembly 30, and a second electrode 30A positioned at aperiphery of the upper assembly 30 of deposition system 1′ as shown inFIG. 1B. In an embodiment, the second electrode 30A is placed beyond anouter edge of the substrate 25. Moreover, electrode 30A may include agas injection assembly configured to inject a plasma generating gas, aswill be further described herein. Power may be coupled to secondelectrode 30A from the first power source 50, or from an independentpower source not shown in FIG. 1B. Where the electrode 30A is poweredfrom the power source 50, a power divider network may be used to ensurethat the power provided on the electrode 30A differs in phase, and/oramplitude, and/or frequency from the power provided on an electrode ofupper assembly 30. The power source supplying power to the electrode 30Amay be any of the configurations described with respect to power source50, or other suitable configurations may be used. For example, electrode30A may comprise a ring electrode, a single-turn coil, or a helical coilcoupled to radio frequency (RF) power. Other inductively coupled devicescan be used to supply an electromagnetic power into a plasma. Forexample, one such device is described in pending U.S. patent applicationSer. No. 10/717,268, attorney docket no. USP03Z0003, entitled “PlasmaProcessing System with Locally-Efficient Inductive Plasma Coupling”. Atypical frequency for the power supply can range from about 0.1 MHz toabout 100 MHz.

Optionally, the deposition system 1 comprises a substrate biasgeneration system configured to generate or assist in generating aplasma during at least a portion of the alternating introduction of thefirst process material and the second process material to processchamber 10. The substrate bias system can include a substrate powersource 52 coupled to the process chamber 10, and configured to couplepower to substrate 25. The substrate power source 52 may include a radiofrequency (RF) generator and an impedance match network, and may furtherinclude an electrode through which RF power is coupled to substrate 25.The electrode can be formed in substrate holder 20. For instance,substrate holder 20 can be electrically biased at a RF voltage via thetransmission of RF power from a RF generator (not shown) through animpedance match network (not shown) to substrate holder 20. A typicalfrequency for the RF bias can range from about 0.1 MHz to about 100 MHz.RF bias systems for plasma processing are well known to those skilled inthe art. Alternately, RF power is applied to the substrate holderelectrode at multiple frequencies.

Although the plasma generation system and the optional substrate biassystem are illustrated in FIG. 1A as separate entities, they may indeedcomprise one or more power sources coupled to substrate holder 20.Further, the power source used to power electrode 30A, as shown in FIG.1B, may be combined with one or both of power sources 50 and 52.

Still referring to FIG. 1A, deposition system 1 comprises substratetemperature control system 60 coupled to the substrate holder 20 andconfigured to elevate and control the temperature of substrate 25.Substrate temperature control system 60 comprises temperature controlelements, such as a cooling system including a re-circulating coolantflow that receives heat from substrate holder 20 and transfers heat to aheat exchanger system (not shown), or when heating, transfers heat fromthe heat exchanger system. Additionally, the temperature controlelements can include heating/cooling elements, such as resistive heatingelements, or thermoelectric heaters/coolers, which can be included inthe substrate holder 20, as well as the chamber wall of the processchamber 10 and any other component within the deposition system 1.

In order to improve the thermal transfer between substrate 25 andsubstrate holder 20, substrate holder 20 can include a mechanicalclamping system, or an electrical clamping system, such as anelectrostatic clamping system, to affix substrate 25 to an upper surfaceof substrate holder 20. Furthermore, substrate holder 20 can furtherinclude a substrate backside gas delivery system configured to introducegas to the back-side of substrate 25 in order to improve the gas-gapthermal conductance between substrate 25 and substrate holder 20. Such asystem can be utilized when temperature control of the substrate isrequired at elevated or reduced temperatures. For example, the substratebackside gas system can comprise a two-zone gas distribution system,wherein the helium gas gap pressure can be independently varied betweenthe center and the edge of substrate 25.

Furthermore, the process chamber 10 is further coupled to a pressurecontrol system 32, including a vacuum pumping system 34 and a valve 36,through a duct 38, wherein the pressure control system 34 is configuredto controllably evacuate the process chamber 10 to a pressure suitablefor forming the thin film on substrate 25, and suitable for use of thefirst and second process materials. As seen in FIG. 1A, the depositionsystem 1 may optionally include a vacuum pump 34A suitable for vacuumpumping through gas injection holes in the upper assembly 30, as will befurther described below. While shown schematically in FIG. 1A, thevacuum pump 34A may include a valve and duct such as that used in vacuumpump 34.

The vacuum pumping systems 34 and 34A can include a turbo-molecularvacuum pump (TMP) or a cryogenic pump capable of a pumping speed up toabout 5000 liters per second (and greater) and valve 36 can include agate valve for throttling the chamber pressure. In conventional plasmaprocessing devices utilized for dry plasma etch, a 300 to 5000 liter persecond TMP is generally employed. Moreover, a device for monitoringchamber pressure (not shown) can be coupled to the process chamber 10.The pressure measuring device can be, for example, a Type 628B Baratronabsolute capacitance manometer commercially available from MKSInstruments, Inc. (Andover, Mass.).

Still referring to FIG. 1A and FIG. 1B, controller 70 can comprise amicroprocessor, memory, and a digital I/O port capable of generatingcontrol voltages sufficient to communicate and activate inputs todeposition system 1 (1′) as well as monitor outputs from depositionsystem 1 (1′). Moreover, the controller 70 may be coupled to and mayexchange information with the process chamber 10, substrate holder 20,upper assembly 30, electrode 30A, first process material supply system40, second process material supply system 42, purge gas supply system44, first power source 50, second power source 52, substrate temperaturecontroller 60, and pressure control system 32. For example, a programstored in the memory may be utilized to activate the inputs to theaforementioned components of the deposition system 1 (1′) according to aprocess recipe in order to perform an etching process, or a depositionprocess. One example of the controller 70 is a DELL PRECISIONWORKSTATION 610™, available from Dell Corporation, Austin, Tex.

However, the controller 70 may be implemented as a general-purposecomputer system that performs a portion or all of the microprocessorbased processing steps of the invention in response to a processorexecuting one or more sequences of one or more instructions contained ina memory. Such instructions may be read into the controller memory fromanother computer readable medium, such as a hard disk or a removablemedia drive. One or more processors in a multi-processing arrangementmay also be employed as the controller microprocessor to execute thesequences of instructions contained in main memory. In alternativeembodiments, hard-wired circuitry may be used in place of or incombination with software instructions. Thus, embodiments are notlimited to any specific combination of hardware circuitry and software.

The controller 70 includes at least one computer readable medium ormemory, such as the controller memory, for holding instructionsprogrammed according to the teachings of the invention and forcontaining data structures, tables, records, or other data that may benecessary to implement the present invention. Examples of computerreadable media are compact discs, hard disks, floppy disks, tape,magneto-optical disks, PROMs (EPROM, EEPROM, flash EPROM), DRAM, SRAM,SDRAM, or any other magnetic medium, compact discs (e.g., CD-ROM), orany other optical medium, punch cards, paper tape, or other physicalmedium with patterns of holes, a carrier wave (described below), or anyother medium from which a computer can read.

Stored on any one or on a combination of computer readable media, thepresent invention includes software for controlling the controller 70,for driving a device or devices for implementing the invention, and/orfor enabling the controller to interact with a human user. Such softwaremay include, but is not limited to, device drivers, operating systems,development tools, and applications software. Such computer readablemedia further includes the computer program product of the presentinvention for performing all or a portion (if processing is distributed)of the processing performed in implementing the invention.

The computer code devices of the present invention may be anyinterpretable or executable code mechanism, including but not limited toscripts, interpretable programs, dynamic link libraries (DLLs), Javaclasses, and complete executable programs. Moreover, parts of theprocessing of the present invention may be distributed for betterperformance, reliability, and/or cost.

The term “computer readable medium” as used herein refers to any mediumthat participates in providing instructions to the processor of thecontroller 70 for execution. A computer readable medium may take manyforms, including but not limited to, non-volatile media, volatile media,and transmission media. Non-volatile media includes, for example,optical, magnetic disks, and magneto-optical disks, such as the harddisk or the removable media drive. Volatile media includes dynamicmemory, such as the main memory. Moreover, various forms of computerreadable media may be involved in carrying out one or more sequences ofone or more instructions to the processor of the controller forexecution. For example, the instructions may initially be carried on amagnetic disk of a remote computer. The remote computer can load theinstructions for implementing all or a portion of the present inventionremotely into a dynamic memory and send the instructions over a networkto the controller 70.

The controller 70 may be locally located relative to the depositionsystem 1 (1′), or it may be remotely located relative to the depositionsystem 1 (1′). For example, the controller 70 may exchange data with thedeposition system 1 (1′) using at least one of a direct connection, anintranet, the Internet and a wireless connection. The controller 70 maybe coupled to an intranet at, for example, a customer site (i.e., adevice maker, etc.), or it may be coupled to an intranet at, forexample, a vendor site (i.e., an equipment manufacturer). Additionally,for example, the controller 70 may be coupled to the Internet.Furthermore, another computer (i.e., controller, server, etc.) mayaccess, for example, the controller 70 to exchange data via at least oneof a direct connection, an intranet, and the Internet. As also would beappreciated by those skilled in the art, the controller 70 may exchangedata with the deposition system 1 (1′) via a wireless connection.

Referring now to FIG. 2A, a deposition system 101 is depicted. Thedeposition system 101 comprises a process chamber 110 having a substrateholder 120 configured to support a substrate 125, upon which the thinfilm is formed. The process chamber 110 further comprises an upperassembly 130 coupled to a first process material supply system 140, asecond process material supply system 142, and a purge gas supply system144. Additionally, the deposition system 101 comprises a first powersource 150 coupled to the process chamber 110 and configured to generateplasma in the process chamber 110, and a substrate temperature controlsystem 160 coupled to substrate holder 120 and configured to elevate andcontrol the temperature of substrate 125. Additionally, depositionsystem 101 comprises a controller 170 that can be coupled to processchamber 110, substrate holder 120, upper assembly 130, first processmaterial supply system 140, second process material supply system 142,purge gas supply system 144, first power source 150, and substratetemperature control system 160. The controller 170 may be implemented,for example, as the controller 70 described with respect to FIG. 1A andFIG. 1B above.

The deposition system 101 may be configured to process 200 mmsubstrates, 300 mm substrates, or larger-sized substrates. In fact, itis contemplated that the deposition system may be configured to processsubstrates, wafers, or LCDs regardless of their size, as would beappreciated by those skilled in the art. Substrates can be introduced toprocess chamber 110 through passage 112, and they may be lifted to andfrom an upper surface of substrate holder 120 via substrate lift system122.

The first process material supply system 140 and the second processmaterial supply system 142 are configured to alternatingly introduce afirst process material to process chamber 110 and a second processmaterial to process chamber 110. The alternation of the introduction ofthe first material and the introduction of the second material can becyclical, or it may be acyclical with variable time periods betweenintroduction of the first and second materials. The first processmaterial can, for example, comprise a film precursor, such as acomposition having the principal atomic or molecular species found inthe film formed on substrate 125. For instance, the film precursor canoriginate as a solid phase, a liquid phase, or a gaseous phase, and itmay be delivered to process chamber 10 in a gaseous phase, and with orwithout a carrier gas. The second process material can, for example,comprises a reducing agent, which may also have atomic or molecularspecies found in the film formed on substrate 125. For instance, thereducing agent can originate as a solid phase, a liquid phase, or agaseous phase, and it may be delivered to process chamber 110 in agaseous phase, and with or without a carrier gas.

The first process material and the second process material are chosen inaccordance with the composition and characteristics of a material to bedeposited on the substrate. For example, during the deposition oftantalum (Ta) as a barrier layer, the first process material can includea solid film precursor, such as tantalum pentachloride (TaCl₅), and thesecond process material can include a reducing agent, such as hydrogen(H₂) gas. In another example, during the deposition of tantalum nitride(TaN) or tantalum carbonitride (TaCN) as a barrier layer, the firstprocess material can include a metal organic film precursor, such astertiary amyl imido-tris-dimethylamido tantalum(Ta(NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃, hereinafter referred to as Taimata®; foradditional details, see U.S. Pat. No. 6,593,484), and the second processmaterial can include a reducing agent, such as hydrogen (H₂), ammonia(NH₃), silane (SiH₄), or disilane (Si₂H₆), or a combination thereof. Inanother example, when depositing tantalum nitride (i.e., TaN_(x)), thefirst precursor can include a tantalum-containing precursor, such asTaCl₅, PDEAT (pentakis(diethylamido) tantalum), PEMAT(pentakis(ethylmethylamido) tantalum), TaBr₅, or TBTDET (t-butyliminotris(diethylamino) tantalum). The second precursor can include a mixtureof H₂ and N₂, or NH₃. Still further, when depositing tantalum pentoxide,the first process material can include TaCl₅, and the second processmaterial can include H₂O, or H₂ and O₂. Other examples of first andsecond process material will be provided below with respect to FIG. 5.

Additionally, the purge gas supply system 144 can be configured tointroduce a purge gas to process chamber 110. For example, theintroduction of purge gas may occur between introduction of the firstprocess material and the second process material to process chamber 110,or following the introduction of the second process material to processchamber 110, respectively. The purge gas can comprise an inert gas, suchas a Noble gas (i.e., helium, neon, argon, xenon, krypton), or nitrogen,or hydrogen. In one embodiment, the purge gas supply system 144 can alsobe configured to introduce a reactive purge gas in to chamber 110 aswill be further described herein.

The first material supply system 140, the second material supply system142, and the purge gas supply system 144 can include one or morematerial sources, one or more pressure control devices, one or more flowcontrol devices, one or more filters, one or more valves, or one or moreflow sensors. As discussed with respect to FIG. 1A and FIG. 1B, the flowcontrol devices can include pneumatic driven valves, electromechanical(solenoidal) valves, and/or high-rate pulsed gas injection valves. Anexemplary pulsed gas injection system is described in greater detail inpending U.S. application 60/272,452, filed on Mar. 2, 2001, which isincorporated herein by reference in its entirety.

Referring still to FIG. 2A, the first process material is coupled toprocess chamber 110 through first material line 141, and the secondprocess material is coupled to process chamber 110 through secondmaterial line 143. Additionally, the purge gas may be coupled to processchamber 110 through the first material line 141 (as shown), the secondmaterial line 143 (as shown), or an independent line, or any combinationthereof. In the embodiment of FIG. 2A, the first process material,second process material, and purge gas are introduced and distributedwithin process chamber 110 through the upper assembly 130 that includesgas injection assembly 180. While not shown in FIG. 2A, a sidewall gasinjection valve may also be included in the processing system. The gasinjection assembly 180 may comprise a first injection plate 182, asecond injection plate 184, and a third injection plate 186, which areelectrically insulated from process chamber 110 by insulation assembly188. The first process material is coupled from the first processmaterial supply system 140 to process chamber 110 through a first arrayof through-holes 194 in the second injection plate 184 and a first arrayof orifices 195 in the first injection plate 182 via a first plenum 190formed between the second injection plate 184 and the third injectionplate 186. The second process material, or purge gas, or both, iscoupled from the second process material supply system 142 or purge gassupply system 144 to process chamber 110 through a second array oforifices 197 in the first injection plate 182 via a second plenum 192formed in the second injection plate 184.

Referring still to FIG. 2A, the deposition system 101 comprises a plasmageneration system configured to generate a plasma during at least aportion of the alternating and cyclical introduction of the firstprocess material and the second process material to process chamber 110.The plasma generation system can include a first power source 150coupled to the process chamber 110, and configured to couple power tothe first process material, or the second process material, or both, inprocess chamber 110. The first power source 150 may be variable andincludes a radio frequency (RF) generator 154 and an impedance matchnetwork 156, and further includes an electrode, such as gas injectionassembly 180, through which RF power is coupled to plasma in processchamber 110. The electrode is formed in the upper assembly 130 and isinsulated from process chamber 110 via insulation assembly 188, and itcan be configured to oppose the substrate holder 120. The RF frequencycan, for example, range from approximately 100 kHz to approximately 100MHz. Alternatively, the RF frequency can, for example, range fromapproximately 400 kHz to approximately 60 MHz. By way of furtherexample, the RF frequency can, for example, be approximately 27.12 MHz.

Optionally, the plasma generation system includes a first electrode inthe upper assembly 130, and a second electrode 130A positioned at aperiphery of the upper assembly 130 as shown in deposition system 101′of FIG. 2B. In an embodiment, the second electrode 130A is placed beyondthe outer edge of the substrate 125. Electrode 130A may also include agas injection assembly configured to inject a plasma generating gas.Power may be the coupled to second electrode 130A from the first powersource 150, or from an independent power source not shown in FIG. 2B.Where the electrode 130A is powered from the power source 150A, a powerdivider network may be used to allow the power provided on the electrode130A to differ from the power provided on an electrode of upper assembly130 in characteristics such as phase, frequency, power level etc. Thepower source supplying power to the electrode 130A may be any of theconfigurations described with respect to power source 150, or othersuitable configurations may be used. For example, electrode 130A maycomprise a ring electrode, a single-turn coil, or a helical coil coupledto radio frequency (RF) power. For example, one such device is describedin pending U.S. patent application Ser. No. 10/717,268, attorney docketno. USP03Z0003, entitled “Plasma Processing System withLocally-Efficient Inductive Plasma Coupling”. A typical frequency forthe power supply can range from about 0.1 MHz to about 100 MHz.

Still referring to FIG. 2A, deposition system 101 comprises substratetemperature control system 160 coupled to the substrate holder 120 andconfigured to elevate and control the temperature of substrate 125.Substrate temperature control system 160 comprises at least onetemperature control element, including a resistive heating element suchas an aluminum nitride heater. The substrate temperature control system160 can, for example, be configured to elevate and control the substratetemperature up to from approximately 350° C. to 400° C. Alternatively,the substrate temperature can, for example, range from approximately150° C. to 350° C. It is to be understood, however, that the temperatureof the substrate is selected based on the desired temperature forcausing ALD deposition of a particular material on the surface of agiven substrate. Therefore, the temperature can be higher or lower thandescribed above.

Furthermore, the process chamber 110 is further coupled to a pressurecontrol system 132, including a vacuum pumping system 134 and a valve136, through a duct 138, wherein the pressure control system 134 isconfigured to controllably evacuate the process chamber 110 to apressure suitable for forming the thin film on substrate 125, andsuitable for use of the first and second process materials. As seen inFIG. 2B, the deposition system 101′ may optionally include a vacuum pump134A suitable for vacuum pumping through gas injection holes in theupper assembly 130, as will be further described below. While shownschematically in FIG. 1B, the vacuum pump 134A may include a valve andduct such as that used in vacuum pump 134A. The valve of vacuum pumpingsystem can be capable of selective pumping of line 141 and 143. Further,the vacuum pump 134A may be coupled to orifices in the peripheralelectrode 130A to provide a vacuum pump feature on this electrode.

Referring now to FIG. 3, deposition system 1/1′/101/101′ (denoted byFIGS. 1A, 1B/FIGS. 2A, 2B reference numeral) can be configured toperform a plasma enhanced atomic layer deposition (PEALD) processaccording to an embodiment of the present invention. FIG. 3 is a timingdiagram for an exemplary PEALD process in accordance with an exemplaryembodiment of the present invention. As seen in this figure, a firstprocess material is introduced to process chamber 10/110 for a firstperiod of time 310 in order to cause adsorption of the film precursor(first process material) on exposed surfaces of substrate 25/125, thenthe process chamber 10/110 is purged with a purge gas for a secondperiod of time 320. Thereafter, a reducing agent (second processmaterial), is introduced to process chamber 10/110 for a third period oftime 330 while power is coupled through the upper assembly 30/130 fromthe first power source 50/150 to the reducing agent as shown by 340. Thecoupling of power to the reducing agent heats the reducing agent, thuscausing ionization and/or dissociation of the reducing agent in order toform a radical that chemically reacts with the first precursor adsorbedon substrate 25/125. When substrate 25/125 is heated to an elevatedtemperature, the surface chemical reaction facilitates the formation ofthe desired film. The process chamber 10/110 is purged with a purge gasfor a fourth period of time. The introduction of the first and secondprocess materials, and the formation of plasma can be repeated anynumber of times to produce a film of desired thickness on the substrate.

While FIG. 3 shows discrete pulses of the first process material, thefirst process material may be a continuous flow, for example on acarrier gas, where such continuous flow will not cause undesirablereaction with the second process material prior to deposition on thesubstrate surface. While FIG. 3 shows plasma generation only during thereduction gas period, a plasma may also be generated during the firstprocess material period in order to facilitate adsorption of the firstprocess material to the substrate surface. Moreover, although the secondprocess material time period 330 and the plasma time period 340 areshown in FIG. 3 to exactly correspond to one another, it is sufficientfor purposes of the present invention that such time periods merelyoverlap, as would be understood by one of ordinary skill in the art.

As discussed in the Related Art section above, one impediment to wideacceptance of ALD processes has been the relatively slow deposition rateof such processes. In particular, conventional ALD processes typicallyrequire a cycle of approximately 15-20 seconds to deposit a single layerof material, with the reduction reaction typically accounting forapproximately 10 seconds of the cycle time. The present inventors havestudied the process parameters of conventional ALD processes in aneffort to reduce this deposition time (or improve the deposition rate).As a consequence, the present inventors have determined that theconventional plasma power of 600 W or less may be increased toaccelerate the reduction reaction time. For example, in performing aPEALD process such as that described in FIG. 3 to prepare a thin,conformal, tantalum-containing film, using tantalum pentachloride as thefirst process material, and hydrogen as the second process material,approximately 1000 W of power was coupled to the hydrogen reducingagent. With this power level, completion of the reduction reaction tosaturation was achieved in approximately 5 seconds, rather than theapproximately 10 seconds typical for a 600 W plasma power process.

For instance, process parameters are provided in Table 1 for anexemplary PEALD process for forming a thin film of tantalum (Ta) usingtantalum pentachloride as the first process material and hydrogen as thesecond process material during the reduction step.

TABLE 1 Carrier TaCl₅ Ar H₂ Ar Time Power P (deg C.) (sccm) (sccm)(sccm) (sec) (W) (Torr) TaCl₅ 140 20 0 500 3 0 Purge 0 0 2000 0 3 0 H₂ 00 2000 0 10 for 1000 0.4 FIG. 4B for FIG. 4A Purge 0 0 0 500 3 0

Table 1 provides columns including, from left to right, the ALD processstep, the temperature set for the evaporation system configured tosublime the first process material, TaCl₅, the flow rate of Ar (carrierAr, sccm) passing through the evaporation system, the flow rate ofhydrogen (H₂ sccm) during the reduction step, the flow rate of Ar (Ar,sccm) coupled directly to the process chamber, the time for each step,the power applied during each step, and the pressure set for each step.Additionally, the tantalum film is formed on a silicon dioxide (SiO₂)substrate using 300 cycles as described in Table 1, while thetemperature of the substrate is set to approximately 240 degrees C.FIGS. 4A and 4B present process data for the exemplary PEALD processdepicted in Table 1.

In FIG. 4A, each process parameter is held constant, including the powerduring the reduction step (i.e., 1000 W), while the time for thereduction step is varied from approximately three (3) seconds to fifteen(15) seconds. When the power is increased to 1000 W, the time for thereduction step can be approximately 5 seconds or greater. At this lattertime duration, the film thickness and the film resistivity becomeconstant with increasing time.

In FIG. 4B, each process parameter is held constant, including the timeduration for the reduction step (i.e., 10 seconds), while the powerapplied during the reduction step is varied from approximately 500 W toapproximately 2000 W. As the power is increased, the film thicknessincreases and the film resistivity decreases. For example, a tantalumfilm having a resistivity less than approximately 460 μΩ-cm can beformed.

Thus, the present inventors have discovered that increasing the plasmapower over the conventional limit of approximately 600 W can improve thedeposition rate of ALD films, as well as film characteristics such asfilm resistivity. Moreover, the present inventors have recognized thatthe use of such a relatively high plasma power provides a more completerelease of byproducts from the first process material layer on thesubstrate, during the reduction reaction when the second processmaterial is introduced to the chamber. Returning to the example above,where tantalum pentachloride is first adsorbed onto the substratesurface, a hydrogen plasma generated at approximately 1000 W willrelease more chlorine from the tantalum pentachloride layer than aplasma generated at 600 W. For example, FIG. 4C shows a decrease in thechlorine content of the tantalum film for the PEALD process describedabove, as the power applied during the reduction step is increased fromapproximately 500 W to approximately 2000 W. Hence, an increase in powerprovides a film that has a reduced amount of chemical by-productimpurities, which results in improved film characteristics such asresistivity or dielectric constant. For example, a tantalum film havinga chlorine content less than 0.95 atomic percent (at. %) can be formed.

For instance, one explanation for the reduced reduction reaction time athigher plasma power is that the increased power provides a higherdensity of radicals in the plasma, such as H⁺ in a hydrogen plasma, thatcan react with the first precursor on the substrate surface. Theavailability of more radicals provides for a shorter saturation time inthe reduction reaction.

Furthermore, for instance, according to another explanation, reductionon the surface can depend on the surface temperature and, hence, thereduction process should depend on temperature according the Arrheniusrelation, i.e., R≅R₀ exp(−E_(activation)/kT_(surface)) It is known thatplasma produces an apparently lower activation energy than theactivation energy in an electrically neutral gas environment. Themechanism for reduced activation energy is caused by ion-neutralinteractions, rather than neutral-neutral interaction. Due to reducedapparent activation energy, more reaction products are generated intime, or saturation occurs sooner.

For example, one interpretation is that an increase in plasma powergenerates a greater reduction in activation energy, whereas less plasmapower generates less reduction or zero change in the activation energy.Assuming that for a first plasma power (P₁), the amount of releasedchlorine (Cl) in time interval (Δt) from tantalum pentachloride (TaCl₅)by hydrogen radicals (H^(•)) is proportional to the reactant(s) densityand to the rate constant with Arrhenius dependence on the temperature,that isΔn _(Cl)(P ₁)=R ₀(P ₁)×n _(H)(P ₁)×n _(TaCl) ₅ ×Δt.

At a second plasma power (P₂), such that (P₂>P₁), the released amount of(Cl) is proportional toΔn _(Cl)(P ₂)=R ₀(P ₂)×n _(H)(P ₂)×n _(TaCl) ₅ ×Δt.

Based on the assumption that (E₂ ^(A)<E₁ ^(A)) at (P₂>P₁), andconsidering (E₂ ^(A)=αE₁ ^(A)) where (α≦1), we can rewrite bothrelations in a form (considering the same time interval)Δn _(Cl)(P _(1,2))=R ₀ exp(−E _(1,2) ^(A) /kT _(1,2))×n _(H)(P _(1,2))×n_(TaCl) ₅ ×Δt.

Now the ratio of released (Cl) densities for both cases becomes

${\frac{\Delta\;{n_{Cl}( P_{2} )}}{\Delta\;{n_{Cl}( P_{1} )}} = \frac{R_{0}{\exp( {{- E_{2}^{A}}/{kT}_{2}} )}{n_{H}( P_{2} )}n_{{TaCl}_{5}}\Delta\; t}{R_{0}{\exp( {{- E_{1}^{A}}/{kT}_{1}} )}{n_{H}( P_{1} )}n_{{TaCl}_{5}}\Delta\; t}},$

e.g.

$\begin{matrix}{\frac{\Delta\;{n_{Cl}( P_{2} )}}{\Delta\;{n_{Cl}( P_{1} )}} = {\frac{n_{H}( P_{2} )}{n_{H}( P_{1} )}{\exp( {- \frac{{E_{2}^{A}T_{1}} - {E_{1}^{A}T_{2}}}{{kT}_{1}T_{2}}} )}}} \\{= {\frac{n_{H}( P_{2} )}{n_{H}( P_{1} )}{{\exp( {\frac{E_{1}^{A}}{{kT}_{1}}\frac{T_{2} - {\alpha\; T_{1}}}{T_{2}}} )}.}}}\end{matrix}$

Deconvolution of the last relation into a Taylor series expansion leadsto

$\frac{\Delta\;{n_{Cl}( P_{2} )}}{\Delta\;{n_{Cl}( P_{1} )}} \cong {{\frac{n_{H}( P_{2} )}{n_{H}( P_{1} )}\lbrack {1 + {\frac{E_{1}^{A}}{{kT}_{1}}\frac{T_{2} - {\alpha\; T_{1}}}{T_{2}}} + {\frac{1}{2}( {\frac{E_{1}^{A}}{{kT}_{1}}\frac{T_{2} - {\alpha\; T_{1}}}{T_{2}}} )^{2}} + \ldots} \rbrack}.}$

The ratio,

${k_{1} \equiv \frac{n_{H}( P_{2} )}{n_{H}( P_{1} )}},$

is always larger than unity, assuming a monotonic increase in hydrogenradicals with plasma power, e.g., k₁≧1. Neglecting higher orders in asum of infinite series, leaving only the first two members,

${1 + {\frac{E_{1}^{A}}{{kT}_{1}}\frac{T_{2} - {\alpha\; T_{1}}}{T_{2}}} + \ldots},$

we can see that

$\frac{T_{2} - {\alpha\; T_{1}}}{T_{2}} \geq 0$(always) for any values of (0<α≦1), and therefore

$\frac{E_{1}^{A}}{{kT}_{1}} > 0.$From the last estimates we can achieve

${\frac{\Delta\;{n_{Cl}( P_{2} )}}{\Delta\;{n_{Cl}( P_{1} )}} \cong {{k_{1}\begin{pmatrix}{where} \\{k_{1} \geq 1}\end{pmatrix}}\lbrack {1 + \begin{Bmatrix}{positive} \\{number}\end{Bmatrix}} \rbrack}},$

that there is always larger amount of chlorine released by hydrogenradicals in the same time interval at higher power, e.g.,Δn_(Cl)(P₂)≧Δn_(Cl)(P₁).

Further yet, for instance, according to another explanation, plasmainteraction with the substrate surface can have an effect on theeffective surface temperature of the substrate due to ion bombardment.Increased plasma power generates a higher V_(pp) (peak-to-peak voltage)on the electrode (such as an electrode in the upper assembly 30, or130), which can cause a higher energy for ions incident on thesubstrate. Higher energy collisions with the substrate surface cangenerate a higher effective surface temperature and accelerates surfacereactions. With time, local temperature is increased, thus saturationoccurs sooner.

FIG. 5 shows a process flow diagram of an ALD process in accordance withan embodiment of the present invention. The process of FIG. 5 may beperformed by the processing system of FIGS. 1A, 1B, or 2A, 2B, or anyother suitable processing system. As seen in FIG. 5, the process beginswhen a substrate, such as a semiconductor substrate, is inserted in aprocess chamber in step 410. For example, the substrate may beelectrostatically clamped to a substrate holder such as the holder 25 or125 described with respect to the systems of FIGS. 1A, 1B, and FIGS. 2A,2B. In step 420, the first process material is provided into the processchamber for depositing on the substrate. The first process material canbe a chemically volatile but thermally stable material that can bedeposited on the substrate surface in a self-limiting manner. The natureof such deposition depends on the composition of the first processmaterial and the substrate being processed. For example, the firstprocess material can be absorbed on the substrate surface.

In step 430, the second process material is provided in the processchamber to provide a reduction reaction with the deposited first processmaterial in order to form a desired film on the substrate surface. Aswould be understood by one of ordinary skill in the art, the first andsecond process materials are selected in accordance with a desired filmto be deposited on the substrate. For example, first and second processmaterials for depositing a tantalum-containing film may include anycombination of the tantalum deposition materials discussed above and thereducing agents discussed above.

In one example, when depositing tantalum (Ta), tantalum nitride, ortantalum carbonitride, the first process material can include TaF₅,TaCl₅, TaBr₅, Tal₅, Ta(CO)₅, Ta[N(C₂H₅CH₃)]₅ (PEMAT), Ta[N(CH₃)₂]₅(PDMAT), Ta[N(C₂H₅)₂]₅ (PDEAT), Ta(NC(CH₃)₃)(N(C₂H₅)₂)₃ (TBTDET),Ta(NC₂H₅)(N(C₂H₅)₂)₃, Ta(NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃, orTa(NC(CH₃)₃)(N(CH₃)₂)₃, and the second process material can include H₂,NH₃, N₂ and H₂, N₂H₄, NH(CH₃)₂, or N₂H₃CH₃.

In another example, when depositing titanium (Ti), titanium nitride, ortitanium carbonitride, the first process material can include TiF₄,TiCl₄, TiBr₄, Til₄, Ti[N(C₂H₅CH₃)]₄ (TEMAT), Ti[N(CH₃)₂]₄ (TDMAT), orTi[N(C₂H₅)₂]₄ (TDEAT), and the second process material can include H₂,NH₃, N₂ and H₂, N₂H₄, NH(CH₃)₂, or N₂H₃CH₃.

As another example, when depositing tungsten (W), tungsten nitride, ortungsten carbonitride, the first process material can include WF₆, orW(CO)₆, and the second process material can include H₂, NH₃, N₂ and H₂,N₂H₄, NH(CH₃)₂, or N₂H₃CH₃.

In another example, when depositing molybdenum (Mo), the first processmaterial can include molybdenum hexafluoride (MoF₆), and the secondprocess material can include H₂.

When depositing copper, the first process material can includeorganometallic compounds, such as Cu(TMVS)(hfac), also known by thetrade name CupraSelect®, available from Schumacher, a unit of AirProducts and Chemicals, Inc., 1969 Palomar Oaks Way, Carlsbad, Calif.92009), or inorganic compounds, such as CuCl. The second processmaterial can include at least one of H₂, O₂, N₂, NH₃, or H₂O. As usedherein, the term “at least one of A, B, C, . . . or X” refers to any oneof the listed elements or any combination of more than one of the listedelements.

In another example, when depositing ZrO₂, the first process material caninclude Zr(NO₃)₄, or ZrCl₄, and the second process material can includeH₂O.

When depositing HfO₂, the first process material can includeHf(OBu^(t))₄, Hf(NO₃)₄, or HfCl₄, and the second process material caninclude H₂O. In another example, when depositing hafnium (Hf), the firstprocess material can include HfCl₄, and the second process material caninclude H₂.

In still another example, when depositing niobium (Nb), the firstprocess material can include niobium pentachloride (NbCl₅), and thesecond process material can include H₂.

In another example, when depositing zinc (Zn), the first processmaterial can include zinc dichloride (ZnCl₂), and the second processmaterial can include H₂.

In another example, when depositing SiO₂, the first process material caninclude Si(OC₂H₅)₄, SiH₂Cl₂, SiCl₄, or Si(NO₃)₄, and the second processmaterial can include H₂O or O₂. In another example, when depositingsilicon nitride, the first process material can include SiCl₄, orSiH₂Cl₂, and the second process material can include NH₃, or N₂ and H₂.In another example, when depositing TiN, the first process material caninclude titanium nitrate (Ti(NO₃)), and the second process material caninclude NH₃.

In another example, when depositing aluminum, the first process materialcan include aluminum chloride (Al₂Cl₆), or trimethylaluminum (Al(CH₃)₃),and the second process material can include H₂. When depositing aluminumnitride, the first process material can include aluminum trichloride, ortrimethylaluminum, and the second process material can include NH₃, orN₂ and H₂. In another example, when depositing aluminum oxide, the firstprocess material can include aluminum chloride, or trimethylaluminum,and the second process material can include H₂O, or O₂ and H₂.

In another example, when depositing GaN, the first process material caninclude gallium nitrate (Ga(NO₃)₃), or trimethylgallium (Ga(CH₃)₃), andthe second process material can include NH₃.

Referring again to FIG. 5, in step 440, more than 600 W ofelectromagnetic power is coupled to the second process material in theprocess chamber in order to facilitate a reduction reaction on thesubstrate. As used herein “electromagnetic power” means RF power,microwave frequency power, light wave power, or any known power suitablefor generating a plasma in a plasma process chamber. In the embodimentof FIGS. 1A, 1B, and 2A, 2B, the electromagnetic power can be coupled tothe process chamber using one or more of the electrodes in the upperassembly and the substrate electrode. The coupling of high power to thesecond process material (i.e., reducing agent) in step 440 heats thereducing agent, thus causing ionization and/or dissociation of thereducing agent in order to form a radical that chemically reacts withthe first precursor adsorbed on the substrate to accelerate thereduction process and reduce impurities within the deposited film asdescribed above. In an embodiment, the power ranges from approximately600 W to approximately 1500 W. In another embodiment, the power isapproximately 1000 W, however, the actual plasma processing power mayvary depending on factors such as the composition and characteristics ofthe film to be deposited. Suitable high power levels that enable ALDdeposition of a film at improved deposition speeds and with reducedimpurities in accordance with an embodiment of the invention can bedetermined by direct experimentation and/or design of experiments (DOE).Other adjustable process parameters such as substrate temperature,process pressure, type of process gas and relative gas flows can also bedetermined by direct experimentation and/or design of experiments (DOE).

The reduction reaction completed by step 440 results in a thin layer ofthe desired film being deposited on the substrate surface. For example,the reduction reaction may result in a thin layer of a barrier layer, aseed layer, an adhesion layer, a gate layer, a metal layer, a metaloxide layer, a metal nitride layer, or a dielectric layer beingdeposited on a feature of the substrate. Once the reduction reactiontakes place, steps 420-440 of FIG. 5 can be repeated to depositadditional layers of material on the substrate until the desiredthickness is achieved, as shown by process flow arrow 450 of FIG. 5.

While not shown in FIG. 5, in an embodiment, a purge gas is introducedto the process chamber between the steps for introducing the firstprocess material and the second process material, as discussed withrespect to FIG. 3. That is, the purge gas can be introduced after thefirst process material and before the second process material, or thepurge gas can be introduced after the second process material and beforethe first process material of a subsequent cycle. The purge gas allowsthe first process material to be expelled from the process chamber byvacuum pumping prior to introduction of the second process material.Similarly, where multiple ALD cycles are executed, a purge gas can beintroduced after the reduction reaction takes place to expel the secondprocess material before introduction of the first process material. Thispurging ensures that the reduction reaction occurs primarily at theadsorbed layer of the first process material on the substrate, ratherthan in the process chamber atmosphere prior to being deposited.

In addition to the effect of a high plasma power level on the depositionof ALD films, the present inventors have considered the potential effectof relatively low plasma power on the deposition of ALD films. In doingso, the present inventors have determined that a low power plasma mayprovide for the removal of residual contaminants in the process chamberand the substrate, prior to the actual reduction reaction taking place.Specifically, introduction of the first process material (the filmprecursor) typically results in this material being adsorbed on theprocess chamber components, such as the chamber walls, as well as on thesubstrate. Further, byproducts of previous reduction reactions may existon the process chamber components. For example, when depositing atantalum-containing film as described above, residual chlorine from thefirst process material is typically present on the substrate and chambercomponents.

During the ALD process, and in particular the plasma-enhanced reductionreaction, materials on the chamber components can be sputtered and cancontaminate the deposited film, which can result in a film having poorproperties. The present inventors have recognized that although a higherplasma power can lead to a greater deposition rate, reduced filmresistivity, and reduced chlorine content in the film (for achlorine-containing precursor), it can also lead to the appearance ofother contaminants in the film arising from the sputtering of processchamber components by large ionized contaminants, such as ionizedchlorine (as opposed to the smaller hydrogen ions in a hydrogen plasmareduction step). For instance, when TaCl₅ is reduced on the substratesurface using a hydrogen plasma, HCl evolves from the surface, which inthe presence of the plasma, dissociates to form ionized chlorine, etc.,which is a large ion and capable of sputtering process chambercomponents. As the plasma power is increased, the sheath voltageadjacent process chamber components can exceed the sputtering thresholdfor the material composition of the process chamber component. Forexample, the electrode in the upper assembly 30, 130, as depicted inFIGS. 1A, 1B, 2A and 2B, can be fabricated from a corrosion resistantmaterial, such as nickel (having a sputtering threshold voltage ofapproximately 143 V) when using chlorine-containing materials. Thus, alow power plasma can effectively release the contaminants from thesubstrate and the process chamber wall such that they can be expelledfrom the chamber by vacuum pumping prior to the application ofrelatively high power that, while facilitating a higher rate reductionreaction on the substrate surface, could sputter the chamber components.

Based on the above recognition of the benefits of using low and highpower plasmas, the present inventors discovered that varying the plasmapower level during an ALD process can provide the dual advantage ofreduced contamination of the ALD film as well as improved depositionrate of the film. FIG. 6 shows a process flow diagram of an ALD processin accordance with an embodiment of the present invention. The processof FIG. 6 may be performed by the processing system of FIGS. 1A, 1B, or2A, 2B, or any other suitable processing system. As seen in FIG. 6, theprocess begins when a substrate, such as a semiconductor substrate, isinserted in a process chamber in step 510. In step 520, the firstprocess material is provided into the process chamber in order to adsorbto the substrate surface. In step 530, the second process material isprovided in the process chamber to provide a reduction reaction with thedeposited first process material in order to form a desired film on thesubstrate surface as discussed above. As would be understood by one ofordinary skill in the art, the first and second process materials areselected in accordance with a desired film to be deposited on thesubstrate. For example, any of the combinations of first and secondprocess materials described herein may be applied to the process of FIG.6.

In step 540 of FIG. 6, a first level of electromagnetic power is coupledto the process chamber in order to generate a plasma for reducingcontaminants in the process chamber. The first level of plasma power maybe as low as the threshold level for generating plasma, and ispreferably not higher than a level determined to disrupt or damage thesubstrate including any deposited films thereon. As would be understoodby one of ordinary skill in the art, the first power level will dependon the material being deposited, as well as when the first level ofpower is applied during the ALD process. The first level of power can becoupled to the process chamber during providing the first processmaterial, providing the second process material and/or providing a purgegas. As discussed above, the first level of power can releasecontaminants from the process chamber and/or substrate, while notexceeding the sputtering threshold for the process chamber components.Thus, in an embodiment, the first level of power is applied to theprocess chamber while the second process material is introduced to theprocess chamber. Alternatively, in another embodiment, the first levelof power is applied to the process chamber to generate a cleaning plasmaduring a purge gas step where the released contaminants can beefficiently vacuum pumped from the process chamber. While not shown inFIG. 6, in an embodiment, a purge gas is introduced to the processchamber between the steps for introducing the first and second processmaterials and/or after the reduction reaction as discussed with respectto FIG. 3. In this regard, the first and/or second levels of plasmapower can be applied during the introduction of the purge gas.

In step 550, a second level of power higher than the first level iscoupled to the process chamber to generate a plasma for facilitating areduction reaction on the substrate surface. Thus, the second level ofpower should be coupled to the process chamber during introduction ofthe second process material, but may also be coupled at other timesduring the ALD process. As with the first power level, the second levelof power is largely dependent on the first and second process materials,as well as the time in the ALD process that the second power level isapplied. In an embodiment, the second level of power is above 600 W toaccelerate the reduction reaction and reduce impurities as describedabove. However, in the embodiments of FIG. 6, it is sufficient that thesecond level of power generates a plasma for facilitating the reductionreaction. Once the reduction reaction takes place, steps 520 to 550 ofFIG. 6 can be repeated to deposit additional layers of material on thesubstrate until the desired thickness is achieved, as shown by processflow arrow 560 of FIG. 6.

FIGS. 7A and 7B show power graphs depicting the power level variation ofpower coupled to the process chamber to generate cleaning and reductionreaction plasmas in accordance with embodiments of the presentinvention. As shown by power curve 610 in FIG. 7A, the plasma power maybe applied to the process chamber in a plurality of discrete levels (twoshown). Specifically, the first power level 620 may be applied to removecontaminants from the substrate and the process chamber components sothat such contaminants can be expelled from the process chamber asdescribed above. As also noted above, the first power level may be aslow as the threshold level for plasma generation, or as high as 600 W,and the second power level 630 is preferably above 600 W and morepreferably about 1000 W or greater in order to accelerate the reductionprocess and reduce contaminants. In one example, the first power levelis not higher than a sputtering threshold for chamber components withinthe chamber as discussed above. As seen in FIG. 7B, the plasma powerlevel may be applied to the process chamber in a continuously changingfashion represented by the power curve 650.

As would be understood by one of ordinary skill in the art, the powercurves of FIGS. 7A and 7B are exemplary, and the varying power maydepend on the composition and characteristic of the film to be depositedby the ALD process. For example, the plasma power of FIG. 7A can includemore than two (2) discrete power levels, and the plasma power of FIG. 7Bmay change in a non-linear fashion. Moreover, a combination of steppedand ramped power can be used to provide the first and second powerlevels of steps 540 and 550 of FIG. 6. Still further, suitable highpower levels that enable ALD deposition of a film at improved depositionspeeds and with reduced impurities in accordance with an embodiment ofthe invention can be determined by direct experimentation and/or designof experiments (DOE). Other adjustable process parameters such assubstrate temperature, process pressure, type of process gas andrelative gas flows can also be determined by direct experimentationand/or design of experiments (DOE).

As noted above, varying plasma power such as that shown in the curves610 and 650 of FIGS. 7A and 7B may be applied to the process chamberduring introduction of the second process material alone, or throughoutthe entire ALD cycle as long as a relatively higher power level isapplied to the second process material to facilitate a reductionreaction. For example, where varying power is applied only duringintroduction of the second process material, initial low power levelsmay release impurities from the substrate and the process chamber walls,while not providing sufficient plasma density to substantiallyfacilitate the reduction reaction at the substrate surface. As the powerincreases in a step as shown in FIG. 7A, or a continuous change as shownin FIG. 7B, the plasma radicals facilitate the reduction reaction in anenvironment having been made cleaner by the initial low power.

In another embodiment, the varying power can occur during other steps inthe ALD cycle and serve dual functions. For example, a first power levelcan be applied during introduction of the first process material toassist in adsorption of the first material to the substrate surface,while also operating to release contaminants from the process chamber. Asecond power level may also be applied during introduction of the secondprocess material and/or a purge gas step to reduce contaminants.Ultimately, the plasma power level is increased to above 600 W duringintroduction of the second process material in order to accelerate thereduction process and reduce contamination in the deposited layer asdiscussed above.

As discussed above, in one embodiment of the present invention an inertpurge gas can be introduced into the process chamber during the ALDprocess. Specifically, as shown in FIG. 3, the purge gas may beintroduced into the process chamber between introduction of the firstand second process materials, and further after introduction of thesecond process material at the end of the ALD cycle. This inert purgegas serves the function of separating the first and second processmaterials to reduce chemical reactions in the chamber environment priorto deposition on the substrate surface, and further to assist inexpelling contaminants removed from the process chamber walls and/orsubstrate surface. In another embodiment of the present invention, areactive gas purge can be performed to further assist in removingcontaminants.

FIG. 8 shows a process flow diagram of an ALD process in accordance withan embodiment of the present invention. The process of FIG. 8 may beperformed by the processing system of FIGS. 1A, 1B, or 2A, 2B, or anyother suitable processing system. As seen in FIG. 8, the process beginswhen a substrate is inserted in a process chamber in step 710. In step720, the first process material is provided into the process chamber inorder to adsorb to the substrate surface as discussed above. In step730, the second process material is provided in the process chamber toprovide a reduction reaction with the deposited first process materialin order to form a desired film on the substrate surface. As discussedwith other embodiments, the first and second process materials areselected in accordance with a desired film to be deposited on thesubstrate and any of the combinations of first and second processmaterials described herein may be applied to the process of FIG. 8.

In step 740, a plasma is generated in the process chamber by couplingelectromagnetic power to the process chamber during introduction of thesecond processing material. The power level coupled to the chamber instep 740 is preferably above 600 W, and, for example, can be about 1000W in order to accelerate the reduction reaction and reduce contaminantsas described above. Moreover, a varying power may be coupled to theprocess chamber in order to provide further reduction of contaminants asdescribed in FIGS. 6 and 7 above. However, in the embodiment of FIG. 8,it is sufficient that a power necessary to generate a plasma is providedin step 740 in order to assist in a reduction reaction of the substrate.

In step 750, a reactive cleaning gas is introduced into the processchamber. Unlike the inert purge gas steps discussed with respect to FIG.3, the reactive cleaning gas chemically reacts with contaminants on theprocess chamber walls and/or the substrate surface to assist in removingsuch impurities from the process chamber. As would be understood by oneof ordinary skill in the art, the composition of the reactive gasdepends largely on the ALD process and, in particular, the contaminantsto be removed from the process chamber. That is, in step 750, a reactivegas is selected to react with the contaminants to be removed from theprocess chamber. Returning again to the example of depositing a tantalumfilm, using tantalum pentachloride as the first process material andhydrogen for the second process material (i.e., reduction reaction),chlorine contaminants may reside on the processing walls and within thedeposited film itself. To remove these chlorine contaminants, ammonia(NH₃) can be introduced to chemically react with the chlorinecontaminants and release them from the walls and/or substrate, so thatthe contaminants can be expelled from the chamber by vacuum pumping.Once the purge step 750 is completed, the process steps 720 to 750 canbe repeated to obtain a desired thickness as shown by arrow 760.

In another embodiment, the process chamber walls may be heated in orderto facilitate a chemical reaction to remove the contaminants. Forexample, when reducing chlorine contaminants as described above, thechamber walls are heated to at least 80 degrees C. In some instances, aplasma may also be generated to facilitate the chemical cleaningreaction. However, such plasma should not cause an undesirable reactionat the substrate surface. Once the purge step 750 is completed, theprocess steps 720 to 750 can be repeated to obtain a desired filmthickness as shown by process arrow 760. While FIG. 8 lists the reactivegas purge step 750 after the reduction reaction takes place in step 740,the reactive gas purge may be done between introduction of the first andsecond process materials as shown in FIG. 3. However, unlike the inertgas purge steps shown in FIG. 3, the reactive gas chemically reacts withcontaminants on the walls of the process chamber and/or substrate toassist in removal of the contaminants from the process chamber. Due tothe insertion of the additional step, the act of expelling the reactiveprocess gas and contaminants may include only a single reactive purgestep per ALD cycle as shown in FIG. 8. Alternatively, the reactive purgegas step may be done only intermittently, such as during every othercycle, or every 3^(rd) cycle. In this regard, the reacting gas purgestep may be done in combination with inert purge steps as described inFIG. 3.

In another embodiment of the present invention, contaminants that affectthe ALD process can be reduced by attracting the contaminants away froma substrate region to a peripheral region of the process chamber.Specifically, generation of a plasma within the substrate region ionizescontaminants that can have a detrimental effect on the film deposited onthe substrate. For example, when depositing a tantalum-containingmaterial as discussed above, chlorine contaminants in the processchamber are ionized by application of plasma power. As such, the presentinventors discovered that generating a separate plasma in a peripheralregion of the process chamber can create a potential difference thatinduces a transport of electrically charged material which removesionized contaminants from the substrate region to a peripheral region ofthe process chamber. The attracted contaminants are then either adheredto the process chamber walls or expelled from the process chamber byvacuum pumping, thereby reducing the effects of the contaminants on thedeposited film.

As described above, when depositing a tantalum film using tantalumpentachloride as a film precursor (first process material) and hydrogenas a reducing agent (second process material), HCl evolves from the filmas a product of the surface reduction reaction. HCl in the presence ofthe plasma is dissociated, and chlorine ions (Cl³¹) can be formed. In anelectronegative (Cl) plasma, the decay of the electronegative plasma(typical for chlorine) following the shutdown of plasma power is suchthat the electrons decay quickly due to their high mobility. In a weaklyelectronegative plasma the negative ions will gradually decay within thesubstrate zone (A) (see FIG. 9A) and the substrate zone (A) will bemaintained at electropositive charge for a short period of time(microseconds) by remaining positive ions. In a stronger electronegativeplasma, the negative ions are decaying over a longer time scale relativeto the electrons due to the diffusive character of their motion(recombination at higher pressures) to the closest surfaces. Since inthe substrate zone (A) the closest surfaces are the substrate surface(25 or 125 in FIGS. 1A, 1B, 2A, or 2B) or the electrode in the upperassembly (30 or 130 in FIGS. 1A, 1B, 2A or 2B), the ions reach thesesurfaces in a shorter time than they would reach the sidewalls of theprocess chamber.

In other words, during the plasma decay, there are two stages: (1) Inthe first stage, the flux of negative ions to the wall is absent and theelectron density decays sharply with time, whereby almost all electronsescape within a finite time from the discharge volume where an ion-ion(electron-free) plasma is formed, and (2) In the second stage, thisplasma decays by an ion-ion ambipolar diffusion mechanism. To providetransport of the ions from the substrate zone (A) towards a peripheralzone (B) (see FIG. 9A), such as the walls of the process chamber (andeventually to a pumping orifice), two plasma regions that interface eachother can be produced in accordance with an embodiment of the presentinvention. The first plasma region substantially coincides withsubstrate zone (A), the second plasma region is surrounding the firstplasma region and substantially coincides with the peripheral zone (B),hence, creating large interface surface.

For example, both plasma regions can be powered by generating plasma inmanner of an overlapping timing sequence. Physical adsorption ofchlorine (more generally, reactive products) does not occur withinsubstrate zone (A) when plasma is on in substrate zone (A). Before theturning the plasma off in the substrate zone (A), the plasma in theperipheral zone (B) is initiated. Once the plasma is initiated in theperipheral zone (B), the plasma in the substrate zone (A) isextinguished and ions from the substrate zone (A) are transported toperipheral zone (B), where there is higher probability to be pumped out.This cycling can be repeatedly applied to an electrode in the upperassembly 30 and electrode 30A in FIG. 1B, or to an electrode in theupper assembly 130 and electrode 130A in FIG. 2B, in the substrate zone(A) and the peripheral zone (B), respectively between the main processsteps to transport residual contaminants out of substrate surface. Forinstance, FIGS. 9B and 9C illustrate two exemplary timing sequences.

As previously discussed, FIGS. 1B and 2B show deposition systems havingan optional peripheral plasma electrode for generating a plasma toattract ionized contaminants to the peripheral zone (B) of the processchamber. Specifically, FIG. 1B shows an upper assembly 30 having a firstelectrode positioned to generate a processing plasma substantially in aregion of the substrate 25, i.e., the substrate zone (A) of FIG. 9A. Inaddition, a peripheral electrode 30A is positioned around a periphery ofthe upper assembly 30, and it is configured to generate a secondaryplasma in the peripheral zone (B) of FIG. 9B. Similarly, FIG. 2B showsan upper assembly 130 that generates a first plasma substantially in aregion of the substrate, i.e., the substrate zone (A), as well as aperipheral electrode 130A positioned around a periphery of the upperassembly 130, and it is configured to generate a secondary plasma in theperipheral zone (B). As shown in FIGS. 1B and 2B, the peripheralelectrodes 30A and 130A are positioned outside of a periphery of thesubstrate 25 and 125, respectively, in order to attract contaminantsbeyond an outer edge of the substrate. Further, the peripheralelectrodes may include gas injection orifices coupled to a vacuumpumping system as will be further described below.

The first plasma region in substrate zone (A) can be formed by theplasma source utilized by PEALD process, such as upper assembly(electrode) 30 in FIG. 1A or upper assembly (electrode) 130 in FIG. 2A.The secondary plasma source is created substantially at the perimeter ofthe process chamber using, for instance, the peripheral electrode 30A or130A depicted in FIGS. 1B and 2B, respectively. The peripheral electrode30A and 130A can be as described above, or they may comprise acylindrical electrode that mimics the process chamber wall, or they maycomprise an annular planar electrode at the top, or bottom, or both ofthe process chamber (either single or two electrodes can be utilized).For instance, FIGS. 10A, 10B, 10C, and 10D illustrate electrodeconfigurations for peripheral electrodes 30A and 130A.

Dimensionally the secondary plasma electrode (30A, 130A) can coincideapproximately with the process chamber dimensions, and have minimaldimensions consistent with the edge of the substrate. Because thiselectrode assists plasma transport from the substrate zone (A) to theperipheral zone (B), a sufficient cross-section for gas flow has to beprovided so as to not restrict pumping speed. Examples of electrodegeometry are shown in FIGS. 10A to 10D. As illustrated in FIG. 10A, aperipheral electrode assembly 1300 comprises a first electrode 1330surrounding the peripheral edge of substrate 1325. The electrodecomprises orifices 1332 configured to permit the passage of processinggases there-through. In FIG. 10B, a peripheral electrode assembly 1300′comprising a second electrode 1340 with orifices 1342 is shown. In FIG.10C, a peripheral electrode assembly 1300″ comprising a third electrode1350 with orifices 1352 is shown, and, in FIG. 10D, a peripheralelectrode assembly 1300″′ comprising the third electrode 1350 is shownin combination with the first electrode 1330.

Each electrode can be biased by an external power source, such as aradio frequency (RF) power generator through a matching network in afrequency range from 100 kHz to 100 MHz. A pulsed direct current (DC)signal (positive or negative polarity, depending upon theelectropolarity of the residual gas) can be used, for example, duringthe operation of the first plasma source in substrate zone (A) (i.e.,electrode 30, or 130 in FIGS. 1A and 2B, respectively) in order toassist a quasi-continuous removal of residual species from the substratezone (A). The electrodes can be fabricated from a suitable metal whichis non-corrosive in the reactive environment. For instance, during RFapplication, they can be coated by a suitable, highly chemicallyresistive ceramic material.

Alternatively, the secondary plasma source can include inductivelycoupled devices to supply electromagnetic power to the peripheral zone(B), such as those inductive devices described in for example, such asdescribed in pending U.S. patent application Ser. No. 10/717,268,entitled “Plasma Processing System with Locally-Efficient InductivePlasma Coupling”.

Other examples of inductive devices include the inductive devicesdepicted in FIGS. 11A, 11B, and 11C, 11D. As illustrated in FIGS. 11Aand 11B, a peripheral inductive electrode assembly 1400 comprises afirst inductive electrode 1430 surrounding the peripheral edge ofsubstrate 1425. The electrode 1430 comprises orifices 1432 configured topermit the passage of processing gases there-through. In FIGS. 11C and11D, a second electrode 1440 with orifices 1442 is shown. A typicalfrequency for the power supply can range from about 0.1 MHz to about 100MHz.

FIG. 12 shows a process flow diagram of an ALD process in accordancewith an embodiment of the present invention. The process of FIG. 12 maybe performed by the processing system of FIGS. 1B or 2B, or any othersuitable processing system. As seen in FIG. 12, the process begins whena substrate is inserted in a process chamber in step 810. In step 820,the first process material is provided into the process chamber in orderto adsorb to the substrate surface, and in step 830, the second processmaterial is provided in the process chamber to provide a reductionreaction with the deposited first process material in order to form adesired film on the substrate surface. As with previous embodimentsdescribed herein, the first and second process materials are selected inaccordance with a desired film to be deposited on the substrate. Forexample, any of the combinations of first and second process materialsdescribed herein may be applied to the process of FIG. 12.

In step 840, electromagnetic power is coupled to the process chamberduring introduction of the second process material in order tofacilitate a reduction reaction as discussed above. In the embodiment ofFIG. 12, the power of step 840 is coupled to the process chamber throughan electrode substantially in the region of the substrate, i.e., thesubstrate zone (A). In the embodiments of FIGS. 1B and 2B, the electrodemay be at least one of the upper assembly electrode and the substrateholder electrode. Power coupled to the process chamber during step 840is preferably above 600 W and can, for example, be approximately 1000 Win order to accelerate the reduction reaction and reduce contaminationas discussed above. Moreover, a varying power may be coupled to theprocess chamber in order to provide further reduction of contaminants asdiscussed above. However, the power coupled during step 840 may be anypower sufficient to maintain a plasma to facilitate the reductionreaction.

In step 850, power is coupled to the process chamber to generate aplasma for ionizing contaminants in the region of the substrate asdescribed above. In an embodiment, step 850 of ionizing contaminants isperformed as a consequence of generating a reduction reaction in step840. That is, the process of generating a plasma in step 840 cannaturally ionize contaminants in the substrate region therebysimultaneously performing step 850. In alternate embodiments, however,the process step for ionizing the contaminants can be performedindependently of the reduction reaction step. For example, processconditioning such as plasma power, chamber environment and chamberpressure may be adjusted from the reduction plasma step in order toprovide ideal ionization for the contaminants.

In step 860, power is coupled to a peripheral electrode such as theelectrode 30A or the electrode 130A of FIGS. 1B and 2B respectively, inorder to generate a plasma in the peripheral zone (B) of the processchamber. However, the peripheral plasma has a characteristic differentfrom the substrate region plasma (i.e., substrate zone (A)) in order togenerate a potential difference that attracts ionized contaminants fromthe substrate zone (A) as discussed above. For example, at least one ofa frequency, phase, or power level of the power applied to theperipheral electrode may be different from that applied to the electrodein the upper assembly (process electrode) in order to achieve thedesired plasma characteristic to provide a potential difference. Inanother embodiment, the peripheral plasma characteristic can be changedby injecting a gas from the peripheral electrode to alter the plasmacomposition in the peripheral region.

For instance, a plasma potential can be established according thehighest (positive) potential at a significant surface area interfacingwith the plasma boundary. Because the electrically biased surfaces in aPEALD system are the substrate electrode (20/120 in FIGS. 1A and 2A),and/or an upper electrode (30/130 in FIGS. 1A and 2A), the minimaldimensions for a peripheral electrode/device are: R_(min)>(1.4-1.6)R_(wafer) for a single planar electrode (see e.g. FIG. 10A), orR_(min)>(1.2-1.4) R_(wafer) for a dual planar electrode (see e.g. FIG.10B), or R_(min)>R_(wafer) and d_(min)>R_(wafer)/2 for a cylindricalelectrode (see e.g. FIG. 10C). In these inequalities, R_(min) is theradius of an inner portion of the peripheral electrode, R_(wafer) is theradius of the wafer and d_(min) is the height of the cylindricalelectrode. In one embodiment, the height of the cylindrical electrode isselected such that the area of the electrode is approximately equivalentto the area of the substrate, however this is not required. Whenoperating the plasma in the substrate zone (A), the plasma potential VAwill be established in the substrate zone (A) (determined mostly bysubstrate area). Thereafter, initiating the peripheral plasma inperipheral zone (B) (timely overlapping the portion of the plasmainterval in substrate zone (A)) will increase the plasma potential inthe substrate zone (A) due to electron loss compensation by theperipheral plasma at the interface between the substrate zone (A) andthe peripheral zone (B). By turning the primary plasma off (in thesubstrate zone (A)), the plasma potential in the substrate zone (A) willbe reduced, or even completely decay leaving only the plasma potentialV_(B) existing in the peripheral zone (B) (determined by secondaryelectrode area). Because plasmas in the substrate zone (A) and theperipheral zone (B) differ in volume and boundary area size the plasmapotentials will differ as well at comparable or equal powers. Byexperimentation one can establish the appropriate plasma potential inthe peripheral zone (B) to maximize the residual gas removal from thesystem.

The peripheral plasma generation step 860 at least partially overlapsthe substrate region plasma generation step 850 (as described above; seeFIGS. 9B and 9C) in order to create the potential difference discussedabove. Thus, in an embodiment where ionizing contaminants results fromthe reduction plasma, the second process material is introduced in step830 while power is applied to the substrate region plasma electrode (insubstrate zone (A)) to perform steps 840 and 850. Once the plasmaassisted reduction reaction and ionization of contaminant(s) begin insteps 840 and 850, the peripheral plasma (in peripheral zone (B)) isgenerated in step 860 to attract the ionized contaminants away from thesubstrate zone (A), as discussed above. Power to the process andperipheral electrodes can then be shut off simultaneously after thereduction reaction takes place, or the plasma in the substrate zone (A)can first be turned off while the peripheral plasma (in peripheral zone(B)) is maintained to attract residual ionized contaminants. After theionized contaminants are expelled from the process chamber, theprocessing steps 820 to 860 can be repeated to obtain a desired filmthickness as shown by process arrow 870.

As noted above, the plasma in the substrate zone (A) and the peripheralzone (B) can be generated independently of the plasma generation step840 for reduction reaction. In addition, while not shown in FIG. 12, aswith previous embodiments, a purge gas can be introduced to the processchamber between the steps for introducing a first process material andthe second process material and also after the reduction reaction, asdiscussed with respect to FIG. 3. The purge gas steps can use an inertgas and/or a reactive gas. Thus, substrate and peripheral plasmas can begenerated in steps 850 and 860 during introduction of the first processmaterial, introduction of a purge gas, or an additional plasmageneration step in the ALD process in order to attract contaminants awayfrom the substrate zone (A). In addition, it is to be understood thatsteps 850 and 860 do not need to be performed for each ALD cycle, andcan be performed at intermittent cycles.

In yet another embodiment of the present invention, contaminants thataffect the ALD process can be removed from the process chamber by vacuumpumping the chamber through gas injection orifices of a gas injectionassembly. Specifically, the present inventors have recognized thatduring generation of a plasma within the processing system, powerapplied to a gas injection assembly causes the plurality of gasinjection orifices to act as “hollow anodes” that attract species of theplasma including ionized contaminants. For example, when depositingtantalum-containing material as discussed above, chlorine contaminantsin the process chamber can be ionized and attracted to hollow anodes ofa gas injection assembly. The present inventors discovered that vacuumpumping the plurality of orifices during plasma generation can reducethe contaminants within the process chamber, thereby reducing theeffects of the contaminants on the deposited film.

As previously discussed, FIGS. 1B and 2B show processing systems havingan optional vacuum pump for pumping ionized contaminants from theprocess chamber through a gas injection assembly. Specifically, FIG. 1Bshows a vacuum pump 34A coupled to the upper assembly 30, which can alsoserve as the gas injection assembly for at least one of the firstprocess material supply system 40, the second process material supplysystem 42, or the purge gas supply system 44. While not shown in FIG.1B, a separate gas injection system, such as a sidewall injection valve,is also included in the process chamber 10 in a manner well known to oneof ordinary skill in the art. During generation of a plasma in theprocess chamber 10, power from the first power source 50 is applied tothe upper assembly 30 having a plurality of gas injection orifices whilevacuum pump 34A is used to pump ionized contaminants, attracted to theorifices by the hollow anode effect, from the process chamber throughthe gas injection orifices.

In the embodiment shown in FIG. 2B, the gas injection assembly 180 inthe upper assembly 130 may include a plurality of sets of orifices forrespective materials. Specifically, in the gas injection assembly 180,the first process material is coupled from the first process materialsupply system 140 to process chamber 110 through a first array ofthrough-holes 194 in the second injection plate 184 and a first array oforifices 195 in the first injection plate 182 via a first plenum 190formed between the second injection plate 184 and the third injectionplate 186. The second process material, or purge gas, or both is coupledfrom the second process material supply system 142 or purge gas supplysystem 144 to process chamber 110 through a second array of orifices 197in the first injection plate 182 via a second plenum 192 formed in thesecond injection plate 184. As also seen in FIG. 2B, the first materialline 141 and the second material line 143 may be coupled to vacuum pump134A, thereby allowing vacuum pumping of the process chamber 110 throughthe first array of orifices, or the second array of orifices, or both.Process chamber 110 may also include a sidewall injection valve. Duringgeneration of a plasma in process chamber 110, vacuum pump 134A is usedto pump ionized contaminants attracted to the orifices.

FIG. 13 shows a process flow diagram of an ALD process in accordancewith an embodiment of the present invention. The process of FIG. 13 maybe performed by the processing system of FIG. 1B or 2B, or any othersuitable processing system. As seen in FIG. 13, the process begins whena substrate is inserted in a process chamber in step 910. In step 920,the first process material is provided into the process chamber in orderto adsorb to the substrate surface, and in step 930, the second processmaterial is provided in the process chamber to provide a reductionreaction. The first and/or second process material may be introduced tothe process chamber through a plurality of orifices in a gas injectionelectrode that is also used to generate a plasma and pump the processchamber as will be discussed further below. Moreover, as with previousembodiments described herein, the first and second process materials areselected in accordance with a desired film to be deposited on thesubstrate, and any of the combinations of first and second processmaterials described herein may be applied to the process of FIG. 13.

In step 940, electromagnetic power is coupled to the process chamberduring introduction of the second process material in order tofacilitate a reduction reaction. In the embodiment of FIG. 13, the powerfor generating a reduction reaction plasma is coupled to the processchamber through a gas injection system having a plurality of gasinjection orifices, as described in FIGS. 1B and 2B. Power coupled tothe process chamber during step 940 is preferably above 600 W and can,for example, be approximately 1000 W in order to accelerate thereduction reaction and reduce contamination as discussed above. However,the power coupled during step 940 may be any power sufficient tomaintain a plasma to assist in the reduction reaction.

In step 950, power is applied to a gas injection electrode to generate aplasma for ionizing contaminants in the process chamber. The powerapplied to the gas injection electrode biases the electrode so that gasinjection orifices also act as hollow anodes in step 950 to attract theionized contaminants as discussed above. In an embodiment, step 950 ofionizing contaminants is performed as a consequence of generating thereduction reaction plasma in step 940. That is, the process of applyingpower to the gas injection electrode to generate a reduction reactionplasma in step 940 can naturally ionize contaminants and create hollowanodes thereby simultaneously performing step 950. In alternateembodiments, however, the process step for ionizing and attractingcontaminants can be performed independently of the reduction reactionstep.

In step 960, the ionized contaminants are vacuum pumped from the processchamber through a plurality of orifices in the gas injection electrode.The vacuum pumping step 960 at least partially overlaps the plasmageneration step 950 in order to expel the ionized contaminants asdiscussed above. Thus, in an embodiment where ionizing the contaminantsresults from the reduction reaction plasma, steps 930, 940, 950 and 960of FIG. 13 occur simultaneously. However, steps 950 and 960 of ionizingand expelling contaminants can be performed independently of thereduction reaction. After the ionized contaminants are expelled from theprocess chamber, the processing steps 920-960 can be repeated to obtaina desired film thickness as shown by process arrow 970.

While not shown in FIG. 13, the embodiment of this figure may includeone or more purge gas steps as described in FIG. 3. Moreover, as notedabove, the plasma and pumping steps can be performed at any time duringthe ALD process in order to clean the process chamber. Thus, the plasmafor ionizing and attracting contaminants can be generated during atleast one of introduction of the first process material, introduction ofthe second process material, introduction of a purge gas, orintroduction of some other material suited for ionizing the contaminantsin the process chamber. While gas injection orifices of the gasinjection electrode are preferably used to perform one or more of theseintroduction steps, orifices used for vacuum pumping during the ionizingplasma cannot be also used for introduction of a process material inwhich the plasma is generated.

For example, in one embodiment, the first process material may beintroduced in step 920 by gas injection orifices on the gas injectionelectrode. Then, in step 930, the second process material is introducedusing a separate gas injection path while power is applied to the gasinjection electrode in step 940 to generate a reduction reaction plasma.The alternative gas injection path may be, for example, the sidewall gasinjection valve discussed in FIG. 1B, or a second set of gas injectionorifices as discussed in FIG. 2B. The reduction reaction plasmagenerated in step 940 also serves to ionize the contaminants in theprocess chamber and attract such contaminants to the gas injectionorifices in step 950. During the plasma assisted reduction reaction ofsteps 930, 940 and 950, the gas injection orifices used to introduce thefirst process material are vacuum pumped in order to remove ionizedcontaminants that have been attracted to the orifices due to the hollowanode affect.

As discussed above, various techniques may be employed within a PEALDprocessing system to remove contaminants such as chlorine from theprocessing system and/or a substrate processed in the PEALD system. Thepresent inventors have recognized, however, that despite these efforts,contaminants can deposit on the ALD film during transfer of thesubstrate from the PEALD process chamber to a separate process chamberfor further processing, such as interconnect metallization. Theinventors have observed that the sheet resistance, after a 400 degreesC. anneal, of film structures consisting of an approximately 10 nm thickCu layer, upon an approximately 6 nm thick layer of tantalum, upon anapproximately 6 nm thick layer of tantalum nitride exhibits asignificant increase when the tantalum layer is prepared with a PEALDprocess utilizing tantalum pentachloride as the film precursor. In thisfilm structure, the Cu and tantalum nitride films are prepared usingionized PVD (i-PVD). For example, when the tantalum film is preparedusing i-PVD, the sheet resistance is approximately 8.04 ohms/square and,when the tantalum film is prepared using PEALD (as described above), thesheet resistance is approximately 145 to 185 ohms/square and metal(copper) agglomeration is observed.

The present inventors have also recognized that the above describedtransfer contamination problems can occur for films deposited bynon-plasma ALD, chemical vapor deposition (CVD), plasma enhancedchemical vapor deposition (PECVD), or any other deposition process. Thatis, despite efforts to reduce contamination within the depositionchamber itself, contaminants can affect the deposited film duringtransfer of the substrate from the deposition process chamber to aseparate process chamber for further processing, such as interconnectmetallization.

Thus, despite cleaning efforts in a PEALD or other deposition chamber,metallization can be deposited on a contaminated ALD or other depositedfilm, leading to operation and reliability problems in the end device.Based on this recognition, the present inventors have discovered thatcontaminants can be further reduced on the substrate by performing aplasma cleaning of the substrate after the substrate is removed from thedeposition system.

FIG. 14 shows a process flow diagram of a substrate process inaccordance with an embodiment of the present invention. The processbegins in step 1010 when the substrate is deposited in a depositionchamber for deposition of a film. For example, the substrate may bedeposited in the system of FIG. 1A or 2A described herein. In step 1020,a deposition process is performed in the deposition process chamber. Inone embodiment, step 1020 is performed to deposit at least one of abarrier layer, a seed layer, an adhesion layer, a gate layer, a metallayer, a metal oxide layer, a metal nitride layer, or a dielectric layeron a substrate. Moreover, where the deposition process is a PEALDprocess, one or more of the PEALD processes described herein toaccelerate the ALD process or reduce contamination may be performed aspart of step 1020 of FIG. 14.

After completion of the deposition process, the substrate having the ALDfilm deposited thereon is transferred to a treatment chamber where aplasma cleaning is performed as shown by step 1030. The plasma cleaningis preferably performed with a plasma characterized by low electrontemperature (less than about 1.5 eV) and high plasma density(>1×10¹²/cm³), that enables substantially damage-free cleaning of thedeposited layer according to the invention. Such process parameterscreate a “soft plasma” that effectively reduces contaminants on thesubstrate surface (i.e., the deposited film such as an ALD film surface)without substantially damaging the deposited film. In step 1040, furtherprocessing is performed on the substrate. For example, step 1040 mayinclude deposition of interconnect metallization on the deposited film.

In one embodiment of the invention, the plasma cleaning step 1030 isperformed in a designated treatment chamber, and then transferred to anadditional process chamber for performing processing step 1040. Forexample, the treatment chamber includes a slotted plane antenna (SPA)plasma source which will be described below.

In another embodiment, the plasma cleaning step 1030 is performed in thesame chamber as the processing step 1040. For example, where processingstep 1040 is a metallization step performed in an ionized physical vapordeposition (i-PVD) chamber, the plasma cleaning step 1030 can beperformed in the i-PVD chamber prior to depositing the metal.Specifically, the i-IPVD process can be provided by an apparatus forsputtering conductive metal coating material from an annular magnetronsputtering target. Sputtering can be accomplished by applying a DC powerto the target and the sputtered material is ionized in a processingspace between a target and a substrate by generating a dense plasma inthe space. The ionized sputter material is then drawn to the substratesurface by applying a bias to the substrate. Where the plasma cleaningstep is performed in the i-PVD chamber, the substrate having andeposited film thereon is first exposed to an inert gas such as argon inthe i-PVD chamber. Power is coupled to the i-PVD chamber to heat theinert gas and generate a plasma for reducing contaminants on thesubstrate surface, as described above. During the plasma cleaningtreatment of the substrate, no power is coupled to the metal target, andthe use of substrate bias power is optional. Once the cleaning step iscompleted, DC power to the metal target and substrate bias power isapplied to perform the i-IPVD metallization process. The inventors haveobserved that the sheet resistance after 400° C. anneal of filmstructures consisting of an approximately 10 nm thick Cu layer, upon anapproximately 6 nm thick layer of tantalum, upon an approximately 6 nmthick layer of tantalum nitride exhibits no increase when the tantalumlayer is prepared with a PEALD process utilizing tantalum pentachlorideas the film precursor and the plasma cleaning is performed. In addition,no copper agglomeration is observed.

FIG. 15 is a simplified block diagram of a processing tool forprocessing a substrate in accordance with an embodiment of the presentinvention. The processing tool 1100 contains substrate loading chambers1110 and 1120, processing systems 1130-1160, a robotic transfer system1170 for transferring substrates within the processing tool 1100, and acontroller 1180 for controlling the processing tool 1100. In oneexample, processing system 1130 can be utilized for pre-processing, suchas cleaning, a substrate, and processing system 1140 can be utilized toperform a deposition process such as an ALD process, a PEALD process, aCVD process, a PECVD process or any other film deposition process. Forexample, processing system 1140 may be implemented as the system of FIG.1 or 2 to perform one or more of the PEALD processes descried herein.

In the embodiment of FIG. 15, processing system 1150 is an i-PVD chamberfor depositing interconnect metallization as discussed above. Processingsystem 1160 is a designated treatment chamber having a plasma source,such as a SPA plasma source, as also discussed. The processing tool 1100can be controlled by a controller 1180. The controller 1180 can becoupled to and exchange information with substrate loading chambers 1110and 1120, processing systems 1130-1160, and robotic transfer system1170.

FIG. 16 is a simplified block-diagram of a plasma processing systemcontaining a slot plane antenna (SPA) plasma source for generating aplasma for reducing contaminants on a deposited film such as an ALDlayer. The plasma produced in the plasma processing system 1200 ischaracterized by low electron temperature (less than about 1.5 eV) andhigh plasma density (>1×10¹²/cm³), that enables substantiallydamage-free cleaning of the ALD layer according to the invention. Theplasma processing system 1200 can, for example, be a TRIAS™ SPAprocessing system, commercially available from Tokyo Electron Limited,Akasaka, Japan. The plasma processing system 1200 contains a processchamber 1250 having an opening portion 1251 in the upper portion of theprocess chamber 1250 that is larger than a substrate 1258. A cylindricaltop plate 1254 made of quartz, aluminum oxide, silicon, or aluminumnitride is provided to cover the opening portion 1251. Gas lines 1272are located in the side wall of the upper portion of process chamber1250 below the top plate 1254. In one example, the number of gas lines1272 can be 16 (only two are which are shown in FIG. 16). Alternately, adifferent number of gas feed lines 1272 can be used. The gas lines 1272can be circumferentially arranged in the process chamber 1250, but thisis not required for the invention. A process gas can be evenly anduniformly supplied into the plasma region 1259 in process chamber 1250from the gas lines 1272.

In the plasma processing system 1250, microwave power is provided to theprocess chamber 1250 through the top plate 1254 via a plane antennamember 1260 having a plurality of slots 1260A. The slot plane antenna1260 can be made from a metal plate, for example copper. In order tosupply the microwave power to the slot plane antenna 1260, a waveguide1263 is disposed on the top plate 1254, where the waveguide 1263 isconnected to a microwave power supply 1261 for generating microwaveswith a frequency of 2.45 GHz, for example. The waveguide 1263 contains aflat circular waveguide 1263A with a lower end connected to the slotplane antenna 1260, a circular (coaxial) waveguide 1263B connected tothe upper surface side of the circular waveguide 1263A, and an outport(bottom surface in FIG. 16) of a coaxial waveguide converter 1263Cconnected to the upper surface side of the circular (coaxial) waveguide1263B. Furthermore, a rectangular waveguide 1263D is connected to theinput port (side surface in FIG. 16) of the coaxial waveguide converter1263C and the microwave power supply 1261.

Inside the circular waveguide 1263B, an axial portion 1262 (or innerconductor) of an electro-conductive material is coaxially provided, sothat one end of the axial portion 1262 is connected to the central (ornearly central) portion of the upper surface of slot plane antenna 1260,and the other end of the axial portion 1262 is connected to the uppersurface of the circular waveguide 1263B, thereby forming a coaxialstructure. As a result, the circular waveguide 1263B is constituted soas to function as a coaxial waveguide. The microwave power can, forexample, be between about 0.5 W/cm² and about 4 W/cm². Alternately, themicrowave power can be between about 0.5 W/cm² and about 3 W/cm².

In addition, in the vacuum process chamber 1250, a substrate holder 1252is provided opposite the top plate 1254 for supporting and heating asubstrate 1258 (e.g., a wafer). The substrate holder 1252 contains aheater 1257 to heat the substrate 1258, where the heater 1257 can be aresistive heater. Alternately, the heater 1257 may be a lamp heater orany other type of heater. Furthermore the process chamber 1250 containsan exhaust line 1253 connected to the bottom portion of the processchamber 1250 and to a vacuum pump 1255.

Still referring to FIG. 16, a controller 1299 includes a microprocessor,a memory, and a digital I/O port capable of generating control voltagessufficient to communicate and activate inputs of the plasma processingsystem 1200 as well as monitor outputs from the plasma processing system1200. Moreover, the controller 1299 is coupled to and exchangesinformation with process chamber 1250, the pump 1255, the heater 1257,and the microwave power supply 1261. A program stored in the memory isutilized to control the aforementioned components of plasma processingsystem 1200 according to a stored process recipe. One example ofprocessing system controller 1299 is a UNIX-based workstation.Alternately, the controller 1299 can be implemented as a general-purposecomputer, digital signal processing system, or any of the controllersdescribed herein. Moreover, the controller 1299 may be locally locatedrelative to the plasma processing system 1200 or it may be remotelylocated relative to the plasma processing system 1200 via an internet orintranet. For additional details, a plasma process system having aslotted plane antenna (SPA) plasma source is described in co-pendingEuropean Patent Application EP1361605A1, titled “METHOD FOR PRODUCINGMATERIAL OF ELECTRONIC DEVICE.”, the entire contents of which is herebyincorporated by reference.

Although only certain exemplary embodiments of inventions have beendescribed in detail above, those skilled in the art will readilyappreciate that many modifications are possible in the exemplaryembodiments without materially departing from the novel teachings andadvantages of this invention. For example, various techniques have beendisclosed herein for improving ALD cycle times and reducingcontamination of ALD films. Any combination or all of these features canbe implemented in a single ALD processing system. Accordingly, all suchmodifications are intended to be included within the scope of thisinvention.

The invention claimed is:
 1. A method for depositing a metallic film ona substrate using a plasma enhanced atomic layer deposition (PEALD)process, comprising: disposing said substrate in a process chamberconfigured to facilitate said PEALD process; introducing a first processmaterial within said process chamber; introducing a second processmaterial within said process chamber after the introduction of the firstprocess material within said process chamber; coupling electromagneticpower to said process chamber during introduction of the second processmaterial in order to generate a plasma that facilitates a reductionreaction between the first and second process materials at a surface ofsaid substrate, the reduction reaction depositing the metallic film onthe substrate in a solid state; and performing a cleaning step, afterthe completion of the reduction reaction between the first and secondprocess materials which deposited the metallic film on the substrate ina solid state, by introducing within the process chamber a thirdmaterial which is a reactive gas that chemically reacts withcontaminants in said process chamber to release the contaminants from atleast one of a process chamber component or said substrate, the cleaningstep being performed between cycles of the PEALD process.
 2. The methodof claim 1, wherein said introducing a first process material comprisesintroducing a process material comprising at least one of TaF₅, TaCl₅,TaBr₅, Tal₅, Ta(CO)₅, PEMAT, PDMAT, PDEAT, TBTDET, Ta(NC₂H₅)(N(C₂H₅)₂)₃,Ta(NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃, Ta(NC(CH₃)₃)(N(CH₃)₂)₃, TiF₄, TiCl₄, TiBr₄,Til₄, TEMAT, TDMAT, TDEAT, Ti(NO₃), WF₆, W(CO)₆, MoF₆, Cu(TMVS)(hfac),CuCl, Zr(NO₃)₄, ZrCl₄, Hf(OBu^(t))₄, Hf(NO₃)₄, HfCl₄, NbCl₅, ZnCl₂,Si(OC₂H₅)₄, Si(NO₃)₄, SiCl₄, SiH₂Cl₂, Al₂Cl₆, Al(CH₃)₃, Ga(NO₃)₃, andGa(CH₃)₃.
 3. The method of claim 1, wherein said introducing a secondprocess material comprises introducing a process material comprising atleast one of H₂, N₂, O₂, H₂O, NH₃, H₂O₂, SiH₄, SiH₆, N₂H₄, NH(CH₃)₂, andN₂H₃CH₃.
 4. The method of claim 1, wherein said coupling electromagneticpower to the process chamber comprises coupling at least 600W of powerto the process chamber.
 5. The method of claim 4, wherein said couplingelectromagnetic power to the process chamber comprises coupling at least1000W of power to the process chamber.
 6. The method of claim 1, furthercomprising heating the walls of said process chamber during saidintroduction of the chemically reactive gas.
 7. The method of claim 6,wherein said heating comprises heating the walls of said process chamberto at least 80° C.
 8. The method of claim 1, wherein said introducing areactive gas comprises introducing the reactive purge gas to saidprocess chamber after introducing said second process material.
 9. Themethod of claim 8 wherein said introducing a reactive purge gas furthercomprises introducing the reactive purge gas to said process chamberafter introducing said first process material and before introducingsaid second process material.
 10. The method of claim 8, furthercomprising introducing an inert purge gas to said process chamberbetween introducing said first process material and introducing saidsecond process material.
 11. The method of claim 1, further comprisingcoupling electromagnetic power to said process chamber to generate aplasma during at least one of said introducing a first process materialor introducing a reactive purge gas.
 12. The method of claim 1, furthercomprising forming at least one of a barrier layer, a seed layer, anadhesion layer, a gate layer, a metal layer, a metal oxide layer, ametal nitride layer, or a dielectric layer on said substrate.
 13. Themethod of claim 1, wherein: said introducing a first process materialcomprises introducing TaCl₅ to said process chamber; said introducing asecond process material comprises introducing H₂ to said processchamber; and said introducing a third material which is a reactive gascomprises introducing NH₃ to said process chamber to react with chlorinecontaminants within the process chamber.
 14. A non-transitory computerreadable medium containing program instructions for execution on asubstrate processing system processor, which when executed by theprocessor, cause the substrate processing system to perform the steps inthe method recited in claim
 1. 15. A non-transitory computer readablemedium containing program instructions for execution on a substrateprocessing system processor, which when executed by the processor, causethe substrate processing system to perform the steps in the methodrecited in claim
 13. 16. A semiconductor device comprising at least oneof a barrier layer, a seed layer, an adhesion layer, a gate layer, ametal layer, a metal oxide layer, a metal nitride layer, and adielectric layer formed by the method recited in claim
 1. 17. Asemiconductor device comprising a metal layer formed by the methodrecited in claim
 13. 18. The method of claim 1, wherein the cleaningstep is independent from the plasma enhanced atomic layer deposition(PEALD) process.
 19. The method of claim 1, wherein the plasma enhancedatomic layer deposition (PEALD) process is complete after the completionof the reduction reaction between the first and second process materialswhich deposited the metallic film on the substrate in a solid state.